Vibrational mode-selective chemistry: Methane dissociation on Ni(100)

摘要

A first-principles full-dimensional model for CH_4 dissociation on Ni(100) is derived using a reaction path formulation. Vibrational excitation of the methane is found to significantly enhance reactivity when the molecule undergoes transitions to the ground or lower-energy vibrational states with the excess energy converted into motion along the reaction path. The v_1 vibration has the largest efficacy for promoting reaction, with the v_3 efficacy smaller, but significant.